New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes,ChemPlusChem

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New-Generation Ligand Design for the Gold-Catalyzed Asymmetric Activation of Alkynes
ChemPlusChem ( IF 3.0 ) Pub Date : 2021-07-12 , DOI: 10.1002/cplu.202100232
Giuseppe Zuccarello _{1,

2} , Imma Escofet _{1,

2} , Ulysse Caniparoli _{1,

2} , Antonio M Echavarren _{1,

2}

Affiliation

Gold(I) catalysts are ideal for the activation of alkynes under very mild conditions. However, unlike allenes or alkenes, the triple bond of alkynes cannot be prochiral. In addition, the linear coordination displayed by gold(I) complexes places the chiral ligand far away from the substrate resulting in an inefficient transfer of chiral information. This poses a significant challenge for the achievement of high enantiocontrol in gold(I)-catalyzed reactions of alkynes. Although considerable progress on enantioselective gold(I)-catalyzed transformations has recently been achieved, the asymmetric activation of non-prochiral alkyne-containing small molecules still represents a great challenge. Herein we summarize recent advances in intra- and intermolecular enantioselective gold(I)-catalyzed reactions involving alkynes, discussing new chiral ligand designs that lie at the basis of these developments. We also focus on the mode of action of these catalysts, their possible limitations towards a next-generation of more efficient ligand designs. Finally, square planar chiral gold(III) complexes, which offer an alternative to chiral gold(I) complexes, are also discussed.

中文翻译：

金催化炔烃不对称活化的新一代配体设计

金 (I) 催化剂非常适合在非常温和的条件下活化炔烃。然而，与丙二烯或烯烃不同，炔烃的三键不能是前手性的。此外，金（I）配合物显示的线性配位使手性配体远离底物，导致手性信息的低效转移。这对金(I)催化的炔烃反应实现高对映体控制提出了重大挑战。尽管最近在对映选择性金（I）催化转化方面取得了相当大的进展，但非前手性含炔小分子的不对称活化仍然是一个巨大的挑战。在此，我们总结了涉及炔烃的分子内和分子间对映选择性金 (I) 催化反应的最新进展，并讨论了这些发展基础上的新手性配体设计。我们还关注这些催化剂的作用模式，以及它们对下一代更有效的配体设计的可能限制。最后，还讨论了方形平面手性金（III）配合物，它提供了手性金（I）配合物的替代品。

更新日期：2021-09-02

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